Perovskite battery
By using a bilayer electron transport layer structure of tin dioxide nanocrystals and dense metal oxides in perovskite solar cells, the problems of high cost and weak interfacial bonding of C60 were solved, thus improving the stability and cost of perovskite solar cells.
Patent Information
- Application Number
- CN202422809430.X
- Authority / Receiving Office
- CN · China
- Patent Type
- Utility models(China)
- Current Assignee / Owner
- Filing Date
- 2024-11-18
- Publication Date
- 2025-11-18
- Estimated Expiration
- 2034-11-18
AI Technical Summary
In existing perovskite solar cells, C60 is expensive as an electron transport layer material and has weak bonding with the perovskite interface, resulting in poor device stability. At the same time, SnO2 nanocrystals prepared by solution method are loose and easily lead to the migration of halide ions, which affects the stability of the cell.
Tin dioxide nanocrystals prepared by solution method are used as the first electron transport layer, and a dense metal oxide second electron transport layer is formed on them by chemical or physical deposition method to block the migration of halide ions and reduce light absorption. The hole transport layer interface is optimized by combining nickel oxide and self-assembled monolayer.
It effectively reduces the cost of the electron transport layer, decreases parasitic absorption in the device, and improves the stability and lifespan of perovskite solar cells, making them suitable for commercial applications.
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Figure CN223568014U_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The utility model relates to the technical field of photovoltaic cell, specifically relates to a kind of perovskite cell. BACKGROUND
[0002] Organic-inorganic metal halide perovskite material is suitable as light-absorbing layer of solar cell by virtue of excellent photoelectric performance and low-cost advantage.
[0003] In single-junction or stacked perovskite cell, fullerene / tin dioxide (C 60 / SnO2) is usually used as double electron transport layer, which is mainly due to the fact that fullerene (C 60 ) has high electron mobility and charge extraction capability, combined with the good hole blocking ability of tin dioxide (SnO2), thus effective electron transport can be achieved. However, in C 60 / SnO2 double-layer electron transport layer, the price of C 60 is expensive, which increases the cost of perovskite cell and hinders the commercial application of perovskite cell. At the same time, C 60 has large absorption in short-wave band, which is not conducive to its application in stacked solar cells based on transverse perovskite structure, such as perovskite-crystalline silicon and perovskite-copper indium gallium selenide (CIGS). Moreover, the interface between C 60 and perovskite is weakly bonded, resulting in poor mechanical stress stability of the device. Therefore, it is necessary to develop an electron transport layer material to replace C 60 for promoting the commercial application of perovskite cell.
[0004] SnO2 has been widely used in perovskite cells due to its low cost, wide band gap, high mobility, and small absorption in 300 nm-1200 nm wave band. In the prior art, it is common to use solution method to directly prepare SnO2 on perovskite to replace C 60 as electron transport layer to reduce manufacturing cost. However, the nanocrystalline SnO2 prepared by current solution method is relatively loose, which can easily lead to migration of halogen ions in perovskite, which is not conducive to achieving high-stability perovskite cell.
[0005] In order to solve the above problems existing in the prior art, there is an urgent need in the field for an improved structure of perovskite cell, which can reduce the cost of electron transport layer, reduce the effect of device parasitic absorption, and also avoid the problem of migration of halogen ions in perovskite, thereby improving the stability of the cell during operation. UTILITY MODEL CONTENT
[0006] The following presents a simplified summary of one or more aspects in order to provide a basic understanding of such aspects. This summary is not an extensive overview of all contemplated aspects, and is intended to neither identify key or critical elements of all aspects nor delineate the scope of any or all aspects. Its sole purpose is to present some concepts of one or more aspects in a simplified form as a prelude to the more detailed description that is presented later.
[0007] In order to overcome the above-mentioned defects existing in the prior art, the utility model provides a perovskite battery can reduce the cost of electron transport layer, reduce the effect of device parasitic absorption, and can also avoid the problem of halogen ion migration in perovskite, thereby improving the stability of the battery.
[0008] Specifically, according to one aspect of the utility model provides a perovskite battery, including: perovskite layer, for absorbing light, generating electron-hole pairs;Electron transport layer, set up in the first surface of perovskite layer, for collecting and transmitting the electron to the first electrode, the electron transport layer includes the first electron transport layer on the upper surface of perovskite layer, the first electron transport layer is tin dioxide nanocrystal, and the second electron transport layer on the upper surface of the first electron transport layer, the second electron transport layer is dense metal oxide deposited, for blocking the halogen ion migration in perovskite layer, and hole transport layer, set up in the second surface of perovskite layer, for collecting and transmitting the hole to the second electrode.
[0009] Further, in some embodiments of the utility model, the thickness of the second electron transport layer is 1-100nm, and the density of the metal oxide is greater than 4.7g / cm 3 .
[0010] Further, in some embodiments of the utility model, the second electron transport layer is a metal oxide made of one or more materials doped with tin dioxide, titanium dioxide, zirconium dioxide and zinc oxide.
[0011] Further, in some embodiments of the utility model, the thickness of the first electron transport layer is 1-100nm, and the size of the tin dioxide nanocrystal is 1-100nm.
[0012] Further, in some embodiments of the utility model, the first electrode is a back electrode located at the bottom of the first surface of the perovskite battery, and the second electrode is a top electrode located at the top of the second surface of the perovskite battery.
[0013] Further, in some embodiments of the present application, the first electrode is a metal electrode for collecting the electrons transmitted from the electron transport layer, and the second electrode is a transparent electrode for collecting the photo-generated current.
[0014] Further, in some embodiments of the present application, the perovskite cell comprises a reverse structure, the hole transport layer is located between the perovskite layer and the transparent electrode for collecting and transmitting the holes to the transparent electrode, and the electron transport layer is located between the perovskite layer and the metal electrode for collecting and transmitting the electrons to the metal electrode.
[0015] Further, in some embodiments of the present application, the perovskite cell comprises a formal structure, the hole transport layer is located between the perovskite layer and the metal electrode for collecting and transmitting the holes to the metal electrode, and the electron transport layer is located between the perovskite layer and the transparent electrode for collecting and transmitting the electrons to the transparent electrode.
[0016] Further, in some embodiments of the present application, the hole transport layer comprises a first hole transport layer and a second hole transport layer, wherein the first hole transport layer is made of a nickel oxide material, and the second hole transport layer is located between the first hole transport layer and the perovskite layer for passivating the perovskite layer.
[0017] Further, in some embodiments of the present application, the perovskite layer has a thickness of 10 nm to 100 μm and a band gap of 0.9 to 3.0 eV. BRIEF DESCRIPTION OF DRAWINGS
[0018] The above features and advantages of the present application can be better understood by reading the following detailed description of embodiments of the present application in conjunction with the drawings, in which each component is not necessarily drawn to scale and components having similar or related functions are designated with like or related reference numerals.
[0019] Figure 1 Fig. 1 shows a reverse structure schematic diagram of a perovskite cell according to some embodiments of the present application; and
[0020] Figure 2 Fig. 2 shows a formal structure schematic diagram of a perovskite cell according to some embodiments of the present application.
[0021] LIST OF REFERENCE NUMERALS
[0022] 100 perovskite cell;
[0023] 110 perovskite layer;
[0024] 120 electron transport layer;
[0025] 121 first electron transport layer;
[0026] 122 second electron transport layer;
[0027] 130 hole transport layer;
[0028] 131 first hole transport layer;
[0029] 132 second hole transport layer;
[0030] 140 second electrode;
[0031] 150 first electrode; and
[0032] 160 substrate. DETAILED DESCRIPTION
[0033] The above objects and other advantages of the present application will become more apparent by describing certain specific embodiments thereof with reference to the attached drawings, in which:
[0034] In the description of the present application, it should be noted that unless specifically stated and limited otherwise, the terms "mounting", "connected", "connecting" or "connection" should be understood broadly, for example, can be fixedly connected, can be detachably connected, or integrally connected; can be mechanically connected, can be electrically connected; can be directly connected, or indirectly connected through an intermediate medium; can be internal communication of two elements. For those skilled in the art, the specific meaning of the above terms in the present application can be understood according to the specific circumstances.
[0035] In addition, "upper", "lower", "left", "right", "top", "bottom", "horizontal", "vertical" used in the following description should be understood as the orientation shown in the paragraph and the related drawings. The relative terms are only used for convenience of description, and do not mean that the device described thereby should be manufactured or operated in a specific orientation, and therefore should not be understood as a limitation of the present application.
[0036] It is to be understood that, although the terms "first", "second", "third", etc. can be used herein to describe various components, regions, layers and / or sections, these components, regions, layers and / or sections should not be limited by these terms, and these terms are only used to distinguish different components, regions, layers and / or sections. Therefore, the first components, regions, layers and / or sections discussed below can be referred to as the second components, regions, layers and / or sections without departing from some embodiments of the present application.
[0037] As described above, in the C 60 In the C 60 The high price increases the cost of the perovskite battery, hindering the commercial application of the perovskite battery. At the same time, due to the C 60 It has a large absorption in the short wave band, which is not conducive to its application in the laminated solar cell based on the transverse perovskite structure, such as perovskite-crystalline silicon and perovskite-copper indium gallium selenide (CIGS). Moreover, the C 60 The interface between the perovskite and the SnO2 is weak, resulting in poor mechanical stress stability of the device. Although in the prior art, SnO2 can be directly prepared on the perovskite by solution method to replace C 60 As an electron transport layer, to reduce the manufacturing cost. However, the nanocrystalline SnO2 prepared by the solution method is relatively loose at present, which can easily lead to the migration of halogen ions in the perovskite, which is not conducive to the realization of high-stable perovskite battery.
[0038] In order to solve the above problems existing in the prior art, the present application provides a perovskite battery, which can reduce the cost of the electron transport layer, reduce the parasitic absorption of the device, and also avoid the problem of halogen ion migration in the perovskite, thereby improving the stability of the battery.
[0039] Please refer to Figure 1 , Figure 1 Fig. 1 shows a schematic diagram of a transverse structure of a perovskite battery according to some embodiments of the present application.
[0040] As Figure 1 shown, in some embodiments of the present application, the perovskite battery 100 can include a perovskite layer 110, an electron transport layer 120 and a hole transport layer 130. The perovskite layer 110 is a light absorption layer, which is used to generate electron-hole pairs after absorbing sunlight. The electron transport layer 120 can be disposed on the first surface of the perovskite layer 110, which is used to collect and transport electrons to the first electrode 150. The hole transport layer 130 can be disposed on the second surface of the perovskite layer 110, which is used to collect and transport holes to the second electrode 140.
[0041] Specifically, the perovskite material of the perovskite layer 110 can generally be a three-dimensional structure ABX3, A is usually a monovalent cation, which can include but is not limited to one or a mixture of several monovalent cations such as cesium (Cs), rubidium (Rb), methylamine (CH3NH3), formamidinium (CH2(NH2)2); B is a divalent cation, which can include but is not limited to one or a mixture of several divalent cations such as lead (Pb), copper (Cu), zinc (Zn), gallium (Ga), tin (Sn), calcium (Ca); X is a monovalent anion, which can include but is not limited to one or a mixture of several monovalent anions such as halogen ions such as iodine (I), bromine (Br), chlorine (Cl), fluorine (F), and pseudo-halogen ions such as thiocyanate ions (SCN).
[0042] As shown in FIG. 1, the perovskite solar cell 100 can further include an electron transport layer 120 disposed on the perovskite layer 110. Figure 1 Specifically, the perovskite solar cell 100 can further include a first electron transport layer 121 and a second electron transport layer 122. The first electron transport layer 121 can be disposed on the upper surface of the perovskite layer 110, and the first electron transport layer 121 can be a solution-prepared tin dioxide nanocrystal. The second electron transport layer 122 can be disposed on the upper surface of the first electron transport layer 121, and the second electron transport layer 122 is a dense metal oxide deposited to block the migration of halogen ions in the perovskite layer 110.
[0043] Specifically, the thickness of the first electron transport layer 121 can be 1-100 nm, and the size of the tin dioxide nanocrystal can be 1-100 nm. In this embodiment, since the intrinsic electron mobility of the metal oxide is generally greater than that of C 60 , and its electron extraction capability is also not lower than that of C 60 Therefore, SnO2 is directly prepared on the first surface (e.g., the upper surface or the lower surface) of the perovskite layer 110 by solution method to replace the traditional C 60 As an electron transport layer, it can also achieve good electron transport effect.
[0044] In addition, when the electron transport layer of the perovskite solar cell uses the traditional C 60 , part of the light is easily absorbed by C 60 , but does not produce effective electron-hole pairs, that is, these absorptions do not contribute to the short-circuit current density in the perovskite solar cell, so it is necessary to minimize the parasitic optical absorption caused by C 60 . In this embodiment, the absorption coefficient of the metal oxide to the ultraviolet, visible, and infrared parts of the light is less than that of C 60 , so the parasitic absorption of the electron transport layer to the light can be effectively reduced.
[0045] As shown in FIG. 1, the perovskite solar cell 100 can further include an electron transport layer 120 disposed on the perovskite layer 110. Figure 1As shown, the second electron transport layer 122 can be prepared by a chemical deposition method of metal oxide. The chemical vapor deposition method can include, but is not limited to, atomic layer deposition (ALD), plasma enhanced chemical vapor deposition (PECVD), and other deposition methods.
[0046] In some alternative embodiments, the second electron transport layer 122 can be prepared by a physical deposition method of metal oxide. The physical vapor deposition method can include, but is not limited to, thermal evaporation, electron beam evaporation, magnetron sputtering, reactive plasma deposition, and other deposition methods.
[0047] The second electron transport layer 122 of metal oxide prepared by the above deposition methods is relatively dense, and thus can block the migration of halogen ions in the perovskite layer 110. The thickness of the second electron transport layer 122 can be 1-100 nm, and the density of the metal oxide prepared by deposition can be greater than 4.7 g / cm 3 The second electron transport layer can include, but is not limited to, one of tin dioxide (SnO2), titanium dioxide (TiO2), zirconium dioxide (ZrO2), and zinc oxide (ZnO), or a metal oxide layer doped with multiple materials.
[0048] In this embodiment, a dense second electron transport layer 122 of metal oxide is prepared on the surface of the first electron transport layer 121 (e.g., SnO2 nanocrystals) prepared by a solution method by a chemical deposition or physical deposition method, to construct a double electron transport layer, which can alleviate the problem of halogen ion migration in the perovskite layer 110 caused by the insufficient density of SnO2 nanocrystals when SnO2 is directly prepared as an electron transport layer on the perovskite layer 110 by a solution method, thereby improving the stability of the battery device.
[0049] Please continue to refer to Figure 1 The preparation method of the perovskite layer 110 in the perovskite solar cell 100 can include, but is not limited to, one or more of spin coating, doctor blade coating, evaporation, printing, spraying, spray pyrolysis, and slot coating. The thickness of the perovskite layer 110 can be 10 nm-100 μm, and the band gap thereof can be 0.9-3.0 eV.
[0050] As Figure 1As shown, the first electrode 150 of the perovskite cell 100 can be a back electrode located at the bottom of the first side of the perovskite cell 100, and the second electrode 140 can be a top electrode located at the top of the second side of the perovskite cell 100. The first electrode 150 can be a metal electrode for collecting electrons transmitted by the electron transport layer 120, and the second electrode 140 can be a transparent electrode for collecting photo-generated current. The second electrode 140 can be made of indium-doped tin oxide (ITO). A transparent glass substrate 160 can be further provided on the second side of the second electrode 140.
[0051] Further, as shown in FIG. 1B, the perovskite cell 100 can include a reverse structure. In the reverse structure, the hole transport layer 130 can be located between the perovskite layer 110 and the second electrode 140 (transparent electrode) for collecting and transporting holes to the second electrode 140 (transparent electrode). The electron transport layer 120 can be located between the perovskite layer 110 and the first electrode 150 (metal electrode) for collecting and transporting electrons to the first electrode 150 (metal electrode). Figure 1
[0052] Preferably, the hole transport layer 130 can further include a first hole transport layer 131 and a second hole transport layer 132. The first hole transport layer 131 can be made of a nickel oxide material and located on the second side (e.g. lower surface) of the perovskite layer 110. However, since the nickel oxide can react with the perovskite layer 110, resulting in low device performance and stability, the second hole transport layer 132 of self-assembled monolayer (SAM) can be provided between the first hole transport layer 131 and the perovskite layer 110 for modifying the nickel oxide and effectively optimizing the nickel oxide / perovskite interface. For example, the simplest structure of TBT-BA can be used to form the densest SAM on the first hole transport layer 131 (nickel oxide), thereby optimizing the NiO X / SAM / perovskite interface, enhancing charge collection, suppressing interface reaction and recombination, and since it has the highest binding energy to perovskite, TBT-BA can also most effectively passivate perovskite.
[0053] Figure 1 The working principle of the perovskite cell 100 in the reverse structure shown in FIG. 1B is as follows. Sunlight is incident from the side of the second electrode 140 (transparent electrode) and first received by the hole transport layer 130. The perovskite layer 110 absorbs sunlight and generates electron-hole pairs, in which the holes are collected and transmitted to the second electrode 140 (transparent electrode) by the hole transport layer 130, while the electrons reach the first electrode 150 (metal electrode) through the electron transport layer 120, thereby forming photo-generated current.
[0054] In other optional embodiments, please refer to Figure 2 , Figure 2 A schematic diagram of the formal structure of a perovskite solar cell according to some embodiments of the present invention is shown.
[0055] like Figure 2 As shown, the perovskite solar cell 200 may also include a formal structure. In the formal structure, a hole transport layer 130 may be located between the perovskite layer 110 and the first electrode 150 (metal electrode) for collecting and transporting holes to the first electrode 150 (metal electrode). An electron transport layer 120 may be located between the perovskite layer 110 and the second electrode 140 (transparent electrode) for collecting and transporting electrons to the second electrode 140 (transparent electrode).
[0056] Figure 2 The perovskite solar cell 200 with the formal structure shown operates as follows: sunlight enters from the second electrode 140 (transparent electrode), passes through the electron transport layer 120, and reaches the perovskite layer 110. After absorbing sunlight, the perovskite layer generates electron-hole pairs. Electrons are collected by the electron transport layer 120 and transported to the second electrode 140 (transparent electrode), while holes travel through the hole transport layer 130 to the first electrode 150 (metal electrode), thereby generating a photocurrent.
[0057] Among the two device structures mentioned above, the inverted perovskite solar cell 100 exhibits higher stability compared to the conventional structure, thus showing greater promise for industrial applications. Furthermore, perovskite solar cells can include single-cell perovskite solar cells with conventional or inverted structures, perovskite / perovskite tandem solar cells, perovskite / crystalline silicon tandem solar cells, and perovskite / copper indium gallium selenide (CIGS) tandem solar cells, etc.
[0058] To more clearly explain the fabrication process of the perovskite solar cell 100, please continue reading... Figure 1 ,by Figure 1 Taking a perovskite solar cell 100 as an example, the fabrication method is introduced. The fabrication method of the perovskite solar cell 100 includes: First, a transparent glass substrate 160 with a thickness of 1.1 mm can be fabricated. Then, a second electrode 140 (transparent electrode layer ITO) with a thickness of 100 nm can be fabricated by magnetron sputtering. Next, a first hole transport layer 131 with a thickness of 15 nm can be fabricated by PVD, and a second hole transport layer 132 SAM (2PACz) can be fabricated on top of it by slot coating. On top of this, a perovskite layer with a thickness of 500 nm can be fabricated as an active layer by slot coating. Then, a first electron transport layer 121 SnO2 nanocrystals with a thickness of 30 nm can be fabricated by slot coating, and then a dense second electron transport layer 122 (SnO2) with a thickness of 15 nm can be fabricated by atomic layer deposition. Finally, a first electrode 150 metallic silver with a thickness of 150 nm can be fabricated by thermal evaporation.
[0059] Those skilled in the art can understand that the specific preparation method and the specific preparation parameters of each layer of the preparation method of the perovskite battery 100 listed above are only a non-limiting embodiment provided by the present application, which aims to clearly show the main concept of the present application and provide a specific scheme for the public to implement, rather than to limit the protection scope of the present application. Alternatively, in other embodiments, those skilled in the art can also use other equivalent methods to prepare each layer based on the concept of the present application to achieve the same technical effect.
[0060] In summary, the present application provides an electron transport layer of a perovskite battery and a perovskite battery, which can reduce the cost of the electron transport layer, reduce the effect of device parasitic absorption, and also avoid the problem of halogen ion migration in perovskite, thereby improving the stability of the battery.
[0061] The previous description of the disclosure is provided to enable any person skilled in the art to make or use the disclosure. Various modifications to the disclosure will be apparent to those skilled in the art, and the general principles defined herein can be applied to other variations without departing from the spirit or scope of the disclosure. Thus, the disclosure is not intended to be limited to the examples and designs described herein, but should be granted the broadest scope consistent with the principles and novel features disclosed herein.
Claims
1. A perovskite cell, characterized in that, The application relates to a perovskite solar cell, comprising: a perovskite layer for absorbing light to generate electron-hole pairs; an electron transport layer arranged on a first surface of the perovskite layer for collecting and transporting the electrons to a first electrode, the electron transport layer comprising a first electron transport layer on an upper surface of the perovskite layer, the first electron transport layer being a tin dioxide nanocrystal, and a second electron transport layer on an upper surface of the first electron transport layer, the second electron transport layer being a dense metal oxide deposited for blocking halogen ion migration in the perovskite layer; and a hole transport layer arranged on a second surface of the perovskite layer for collecting and transporting the holes to a second electrode. The second electron transport layer is a metal oxide layer made of one of tin dioxide, titanium dioxide, zirconium dioxide and zinc oxide.
2. The perovskite cell of claim 1, wherein, The thickness of the second electron transport layer is 1-100 nm, and the density of the metal oxide is greater than 4.7 g / cm 3 .
3. The perovskite cell of claim 1, wherein, The thickness of the first electron transport layer is 1-100 nm, and the size of the tin dioxide nanocrystal is 1-100 nm.
4. The perovskite cell of claim 1, wherein, The first electrode is a back electrode at the bottom of a first surface of the perovskite solar cell, and the second electrode is a top electrode at the top of a second surface of the perovskite solar cell.
5. The perovskite cell of claim 1, wherein, The first electrode is a metal electrode for collecting the electrons transported by the electron transport layer, and the second electrode is a transparent electrode for collecting photo-generated current.
6. The perovskite cell of claim 5, wherein, The perovskite solar cell comprises a reverse structure, the hole transport layer is arranged between the perovskite layer and the transparent electrode for collecting and transporting the holes to the transparent electrode, and the electron transport layer is arranged between the perovskite layer and the metal electrode for collecting and transporting the electrons to the metal electrode.
7. The perovskite cell of claim 6, wherein, The perovskite solar cell comprises a formal structure, the hole transport layer is arranged between the perovskite layer and the metal electrode for collecting and transporting the holes to the metal electrode, and the electron transport layer is arranged between the perovskite layer and the transparent electrode for collecting and transporting the electrons to the transparent electrode.
8. The perovskite cell of claim 6, wherein, The hole transport layer comprises a first hole transport layer made of a nickel oxide material and a second hole transport layer arranged between the first hole transport layer and the perovskite layer for passivating the perovskite layer.
9. The perovskite cell of claim 1, wherein, The thickness of the perovskite layer is 10 nm-100 mu m, and the band gap is 0.9-3.0 eV.
10. The perovskite cell of claim 1, wherein,